Polymeric compounds condensed from epichlorhydrin and a bifunctional amino compound,and method of production



Patented June 10, 1952 OFFICE,

POLYMERIC COMPOUNDS CONDENSED FROM EPICHLORHYDRIN AND A BI- FUNCTIONAL AMINO COMPOUND, AND METHOD OF PRODUCTION Albert Stanley Carpenter, Sutton Coldfield, Birmingham, and Eric R. Wallsgrove, Coventry, England, assignors to Courtaulds Limited, London, England, a British company No Drawing. Application February 15, 1950, Se-

rial No. 144,373. In Great Britain March 2,

12 Claims. (01. 26042) This invention relates to the production of polymeric compounds and to the production from such compounds of threads, fibres, filaments and the like, hereinafter generally referred to as threads.

It is known that epichlorhydrin may be reacted with aliphatic, aromatic or heterocyclic secondary amines to produce non-polymeric products; for example British Patent Specification No. 275,622 describes the reaction of epichlorhydrin and secondary amines to form a-tertiaryaminoepihydrins which are then reacted with bases to form unsymmetrically substituted diaminopropanols.

The specification of application Serial No. 124,944, filed 1 November 1949 describes a process for the production of thermoplastic resins by heating substantially equimolecular proportions of epichlorhydrin and at least one aromatic dihydroxy compound in which the hydroxyl groups are phenolic and the carbon atoms linked to the hydroxyl groups are separated by at least one other carbon atom, together with a quantity of an alkali such that the ratio of the number of molecules of alkali to the number of molecules of the dihydroxy compound is at least 1.0, the heating being continued until a fibre-forming resinous product is obtained.

French Specification No. 933,219 describes the production of resinous products suitable for use as anion-active agents by condensing at least 2 mols of an alpha-chloro, beta, gamma-epoxy compound such as epichlorhydrin with one mol of a polyalkylene polyamine, preferably in the presence of a strong alkali.

The object of the present invention is to produce a novel class of polymeric compounds which are in general suitable for the production of threads.

In accordance with the present invention, a process for the production of polymeric compounds comprises heating together, in substantially equimolecular proportion, epichlorhydrin and a bifunctional compound having as one of its functional groups a secondary amine group and as the other functional group a secondary amine group or a hydroxyl group. The functional groups of these bifunctional compounds are separated by at least 4 carbon atoms, and the compounds contain either a benzene ring or a saturated heterocyclic ring structure containing 5 carbon and one nitrogen atoms. According to the invention, the epichlorhydrin and the bifunctional compound are heated together with an alkali in an amount which is at least substantially the chemical equivalent of the chlorine content of the epichlorhydrin used.

In accordance with further embodiments of the present invention, the bifunctional secondary amino compound as defined is partly replaced, for example by a dihydric phenol as used in application Serial No. 124,944 or by a monohydroxy benzoic acid such as parahydroxy benzoic acid whereby mixed polymeric products are obtained. I

The present invention therefore also includes 1 a process for the production of mixed polymeric products which comprises heating together epichlorhydrin, a bifunctional compound having a' secondary amine group as one of its functional groups and as the other functional group a group chosen from the'class consisting of secondary amine groups and hydroxyl groups, the functional groups being separated by at least four carbon atoms, said compounds containing either a benzene ring or a saturated heterocyclic'ring structure containing five carbon and one nitrogen atoms, an aromatic dihydroxy compound in which the hydroxyl groups are phenolic and the carbon atoms linked to the hydroxyl groups are separated by at least one other carbon atom, and an alkali in an amount which is at least the chemical equivalent of the chlorine content of the epichlorhydrin used, the combined proportions of the said bifunctional compound and the said aromatic dihydroxy compound used being substantially the equimolecular equivalent of the epichlorhydrin used. 7

The invention also includes a process for the production of mixed polymeric products which comprises heating together epichlorhydrin, a monohydroxy benzoic acid, a bifunctional compound having a secondary amine group as one of its functional groups and as the other functional group a group chosen from the class consisting of secondary amine groups and hydroxyl groups the functional groups being separated by rates. .for example by first reacting the epichlorhydrin "with from 50 to 100 per cent of the bifunctional bon and one nitrogen atoms; and an alkali in an amount which is at least the chemical equivalent of the chlorine content of the epichlorhydrin used, the combined proportions of the said bifunctional compound and the monohydroxy benzoimacidused .being substantially the equimolecular equivalent of the epichlorhydrin used.

In making mixed polymeric products according to the invention the bifunctional secondary amino compound as defined preferably forms at least per cent of the mixture which is reacted with the epichlorhydrin. and the; alkali.

Suitable secondary amino bifunctional compounds for use in the present invention are- 4,4- dipiperidyl CH CH; CHECH NH CHCE /NH CHrC: GEE-CH1 para-methylaminophenol and other N-alkylsubstituted amino phenols, and bis-4,4-(N- methylaminophenyl) methane, HsC-HN Suitable dihydric phenols for-use in making mixed polymeric products are 'hydroqui-none,

resorcinol and 3,3 or 1 4,4 'dihydroxy diph'enyls.

The process accordin to the invention for makin polymericyproducts may be effected in a 'single'stagereaction by heating the epichlorhydrain, the bifunctional secondary-amino com-- 1 pound and the'alkali together, preferably under a reflux condenser, until a resinous polymer sepa- A two-stage reaction may also beused,

compound as defined and then heating the prod- "uct'with the alkalia-nd any remaining bifunc- --tional compound until a resinous polymer separates; in an'alternative two-stage reaction, one molof ,the' bifunctional compound may be first reactedwith two mols of epichlorhydrin and its equivalent of alkali to form a di-epoxide compound'whieh is thenheated with a further mol of the bifunctional compound containing a small "proportion of an alkali catalyst.

Mixed polymeric products may beprepared according to .theinventionrby heating the four-re- V actants. as defined together, preferably under a reflux condenser, until a resinous mixed polymer separates. Two-stage processes may also be ..used. For-example the .bifunctional secondaryamino-compoundas definedmay be used .in one stageandardihydricphenolas definedor a mono- ..hydroxy .benzoicaoid usedin the. other stage;

, thus. 1. molof the dihydric phenol, 2 .mols of epichlorhydrinand. 2. .mole .of alkali may be reacted together in the .ifirststage to form anarcmatic bis-glycidyl etherby the method described by Wernerand Farenhorst -(Receuil .des .Travaux .Ghimique ,de Pays..Bas,.vol..67. (-1948) ,lpages 438 to. r441) .and then. reacting the. ,bis-glycidyl ether withrlmoliof the bifunctional secondary-amino compound toform aresinous mixed polymeric 7 .product. Alternativelyrmixturesof .thebifuncitional compound with-a dihydric phenol as .de-

iinedor with ahydroxy benzoic acid maybe used inpbothi stages.

.Theprocesses according to the invention are preferably effected in the presence of a diluent such .as aqueous alcohol.

The epichlorhydrin may be formedin situ by using alphaor beta-glycerol dichlorhydrin, or a mixture of both, with one molar equivalent of caustic alkali, in place of the epichlorhydrin. In this case, the caustic alkali used to react with the glycerol chlorhydrin is additional to the alkali required to efiect the reaction according to the invention.

The polymersobtained according to the invention are in general thermoplastic products of high =molecular weight which can usually be drawn ormelt-spun to form threads generally capable ofbei-ng cold-drawn.

The-invention is illustrated by the following .iExamples in which the parts are by weight:

i g Example 1 lll'lwparts' (11mm) of epichlorhydrin, a boiling :s'o'lutioniof mar-parts (1 mol) of 4,4, dipiperidyl in 160 parts of ethylalcohol and a cold solution of 4.55 par'ts (1.04 mol) of caustic soda in parts of water were mixed together and heated for 3 hours under a reflux condenser. At the end of i this time a finely-divided precipitate had formed;

the pasty mass was poured into twice its volume of water, filtered and the precipitate was washed three times-with hot water and dried at 100 centigrade.

The polymereobtained had-an intrinsic viscosity in a 1 per cent solution in meta cresol of 0A2-and when heated was capable of being drawn into Example '2 A product consisting of themixed stereoisomers of 1: 4 bis (2 :3 epoxypropoxy) benzene (otherwise known ashydroquinone bis-glycidyl ether) was prepared from 1 mol of hydroquinone, '2'mols of epichlorhydrin and 2 mols of caustic soda by the .heatedunderreflux for 3 hours.

method described by Werner and Farenhorst (-Receuil des Travaux Chimique de Pays Bas. vol; 67 (1948), pages438 to 441) and 12 parts of this product, 9.15 parts of 4,4'-dipiperidyl,' 0.25 part of caustic soda (as'catalyst) and parts of ethyl alcohol were mixed and heated under a reflux condenser for 1 hours, at the end of which time a finely-divided cream-coloured solid had separated. This solid was filtered off, washed with ethyl alcohol and then with water and finally-dried first at centigrade and then in a vacuum desiccator.

Example 3 icondenser, the reaction mixture being heated un 1 der reflux andstirred throughout. When all the caustic soda hadibeen added the mixture was The product had. separated asra plastic mass which was-separated, Washed three times with boiling water and dried.

The product. melted-at approximately centigrade and when molten was readily drawn out into'fibres.

Example 4 13.6 parts (.82 mol) of 4,4-dipiperidyl, 2.2 parts of hydroquinone (.2 mol), 9.25 parts of epichlorhydrin (1 mol), 4.4 parts'of caustic soda (1.1 mol), 80 parts of alcohol and parts of water were mixed and heated under reflux for 7 hours with continuous vigorous stirring. The product which separated was a viscous mass adhering to the sides of the vessel; 200 parts of water were added, the product separated, washed four times with boiling water and dried. The product was a dark thermoplastic polymer.

Ezmmple 5 15.4 parts (0.93 mol) of 4,4'-dipiperidyl, 1.38 parts (0.1 mol) of para-hydroxy-benzoic acid, 9.25 parts (1 mol) of epichlorhydrin, 4.4 parts (1.1 mol) of caustic soda, 80 parts of alcohol and 10 parts of water were mixed and heated under reflux for six hours with vigorous stirring. The reaction mixture was diluted with 500 parts of water, brought to the boil and filtered hot to separate the product which was washed twice with boiling water and dried.

The product was an oil-white fibre-forming thermoplastic powder which softened at 200 centigrade. Its intrinsic viscosity in a 1 per cent solution in meta-cresol was 0.41.

The term cyclic amino compound is used in the claims to include compounds containing either a benzene ring structure or a saturated heterocyclic ring structure consisting of five carbon atoms and a single nitrogen atom.

What we claim is:

1. A. process as claimed in claim 5, wherein the epichlorhydrin is reacted with from 50 to 100 per cent of the said bifunctional compound and the product is heated with the alkali and up to 50 per cent of the bifunctional compound.

2. A process as claimed in claim 5, wherein the bifunctional compound used is 4,4-dipiperidyl.

3. A process as claimed in claim 5, wherein the bifunctional compound used is para-methyl-aminophenol.

4. A process as claimed in claim 5, wherein the bifunctional reactant is a mixture of any of said bifunctional amino compounds and an aromatic dihydroxy compound in which the hydroxyl groups are phenolic and the carbon atoms linked to the hydroxyl groups are separated by at least one other carbon atom and wherein 1 mol of the aromatic dihydroxy compound is reacted with 2 mols of epichlorhydrin and 2 mole of alkali to form an aromatic bisglycidyl ether and the bisglycidyl ether so obtained is reacted with 1 mol of the said bifunctional compound to form a resinous mixed polymeric product.

5. A process for the production of polymeric compounds which comprises heating together in .substantially equimolecular proportions, epichlorhydrin and a bifunctional reactant selected from the group consisting of (l) bifunctional amino compounds containing a benzene ring and in which both functional groups are secondary amino groups and are separated by at least four carbon atoms, (2) bifunctional amino compounds containing a saturated heterocyclic ring structure having five carbon and one nitrogen atoms, and in which both functional groups are secondary amino groups separated by at least four carbon atoms, (3) bifunctional amino compounds containing a benzene ring, and in which one functional group is a secondary amine and one functional group is an hydroxyl group, said functional groups being separated by at least four jcarbon atoms and (4) mixtures of any of said bifunctional ,amino compounds and a compound selected'from the group consisting of (a) arodihydroxy compound in which the hydroxyl groups are phenolic and the carbon atoms linked to the hydroxyl groups are separated by at least one other carbon atom.

7. A process as claimed in claim 6, wherein the aromatic dihydroxy compound used is hydroquinone.

8. A process for the production of polymeric compounds which comprises heating together epichlorhydrin, 4,4'-dipiperidyl and an aromatic dihydroxy compound in which the hydroxyl groups are phenolic and the carbon atoms linked to the hydroxyl groups are separated by at least one other carbon atom and an alkali in an amount which is at least the chemical equivalent of the chlorine content of the epichlorhydrin used, the combined proportions of said 4,4'-dipiperidy1 and. said aromatic dihydroxy compound being substantially the equimolecular equivalent of the epichlorhydrin used.

9. A process as claimed in claim 5, wherein the bifunctional reactant used is a mixture of said bifunctional amino compounds and. a monohydroxy benzoic acid.

10. A process as claimed in claim 9, wherein the monohydroxy benzoic acid used is parahydroxy benzoic acid.

11. A process for the production of polymeric compounds which comprises heating together epichlorhydrin, 4,4'-dipiperidy1, a monohydroxy benzoic acid, and an alkali in an amount which is at least the chemical equivalent of the chlorine content of the epichlorhydrin used, the combined proportions of the 4,4'-dipiperidyl and the monohydroxy benzoic acid being substantially the equimolecular equivalent of the epichlorhydrin used.

12. A composition of matter comprising a polymeric compound obtained by heating together in substantially equimolecular proportions epichlorhydrin and a bifunctional reactant selected from the group consisting of (1) bifunctional amino compounds containing a benzene ring, and in which both functional groups are secondary amino groups separated by at least four carbon atoms, (2) bifunctional amino compounds containing a saturated heterocyclic ring structure having five carbon and one nitrogen atoms, and in which both functional groups are secondary amino groups separated by at least four carbon atoms, (3) bifunctional amino compounds containing a benzene ring, and in which one functional group is a secondary amine and one functional group is an hydroxyl group, said functional groups being separated by at least four carbon atoms, and (4) mixtures of any of said hifunctional amino compounds and a compound selected from the group consisting of (a) aromatic dihydroxy compounds in which the hydroxyl groups are phenolic and the carbon atoms linked to the hydroxyl groups are separated by at used.

A. STANLEY CARPENTER. E. R. WALLSGROVE.

REFERENCES CITED "The following references are of record in the- 0 file of this patent:

UNITED STATES PATENTS Number Number Name Date Bradley Mar. 14, 1950 FOREIGN PATENTS Country Date Australia, 'Ma-y 19, 1947 

12. A COMPOSITION OF MATTER COMPRISING A POLYMERIC COMPOUND OBTAINED BY HEATING TOGETHER IN SUBSTANTIALLY EQUIMOLECULAR PROPORTIONS EPICHLORHYDRIN AND A BIFUNCTIONAL REACTANT SELECTED FROM THE GROUP CONSISTING OF (1) BIFUNCTIONAL AMINO COMPOUNDS CONTAINING A BENZENE RING, AND IN WHICH BOTH FUNCTIONAL GROUPS ARE SECONDARY AMINO GROUPS SEPARATED BY AT LEAST FOUR CARBON ATOMS, (2) BIFUNCTIONAL AMINO COMPOUNDS CONTAINING A SATURATED HETEROCYCLIC RING STRUCTURE HAVING FIVE CARBON AND ONE NITROGEN ATOMS, AND IN WHICH BOTH FUNCTIONAL GROUPS ARE SECONDARY AMINO GROUPS SEPARATED BY AT LEAST FOUR CARBON ATOMS, (3) BIFUNCTIONAL AMINO COMPOUNDS CONTAINING A BENZENE RING, AND IN WHICH ONE FUNCTTIONAL GROUP IS A SECONDARY AMINE AND ONE FUNCTIONAL GROUP IS AN HYDROXYL GROUP, SAID FUNCTIONAL GROUPS BEING SEPARATED BY AT LEAST FOUR CARBON ATOMS, AND (4) MIXTURES OF ANY OF SAID BIFUNCTIONAL AMINO COMPOUNDS AND A COMPOUND SELECTED FROM THE GROUP CONSISTING OF (A) AROMATIC DIHYDROXY COMPOUNDS IN WHICH THE HYDROXYL GROUPS ARE PHENOLIC AND THE CARBON ATOMS LINKED TO THE HYDROXYL GROUPS ARE SEPARATED BY AT LEAST ONE OTHER CARBON ATOM AND (B) MONOHYDROXY BENZOIC ACIDS; AND AN ALKALI IN AN AMOUNT WHICH IS AT LEAST THE CHEMICAL EQUIVALENT OF THE CHLORINE CONTENT OF THE EPICHLORHYDRIN USED. 